TWI724102B - Solvent composition, cleaning method, coating film forming composition, and coating film forming method - Google Patents

Abstract

The present invention provides a solvent composition containing tDCE that does not adversely affect the global environment, has high solubility, is non-flammable, and can maintain the initial non-flammability even if it is used with a phase change, and its use The method for cleaning articles of the solvent composition, and provides a composition for forming a coating film that does not have an adverse effect on the global environment when using volatile components, has high safety due to non-combustibility, and can form a homogeneous coating film, and A method of forming a homogeneous coating film using the composition for forming a coating film. A solvent composition containing: tDCE; the first HFE (containing at least one HFE selected from HFE-347pc-f, HFE-365mf-c and HFE-467sc-f) with a boiling point of 40~65°C; and boiling point The second HFE at 70~120℃; relative to the total amount of tDCE, the first HFE and HFE-569s1, the ratio of tDCE is 65~80% by mass, the ratio of the first HFE is 5-25% by mass, and the ratio of the second HFE The ratio is 5-25% by mass.

Description

Solvent composition, cleaning method, coating film forming composition, and coating film forming method

FIELD OF THE INVENTION The present invention relates to a solvent composition, a cleaning method using the solvent composition, a coating film forming composition using the solvent composition as a diluting coating solvent, and a coating film forming method using the coating film forming composition .

BACKGROUND OF THE INVENTION In the past, in the manufacture of ICs, electronic parts, precision mechanical parts, optical parts, etc., in order to remove flux, processing oil, wax, mold release agent, dust, etc. attached to the parts, fluorine-based solvents were widely used for parts Precision wash. In addition, in the method of applying a composition in which various coating film forming components such as a lubricant are dissolved in a solvent to the surface of an article and then evaporating the solvent to form a coating film, a fluorine-based solvent is commonly used as a solvent.

As for the above-mentioned fluorine-based solvents, it has high solubility in processing oils and lubricants and other non-volatile compounds, non-flammability, low toxicity, good stability, non-corrosion to metal, plastic, elastomer and other substrates, and chemical and From the viewpoint of good thermal stability, chlorofluorocarbons (hereinafter referred to as "CFC"), hydrofluorochlorocarbons (hereinafter referred to as "HCFC"), etc. are often used.

However, because CFC and HCFC are chemically extremely stable, they have a long life in the troposphere after gasification and will diffuse into the stratosphere. Therefore, there is a problem that CFC or HCFC that reaches the stratosphere is decomposed by ultraviolet rays to generate chlorine free radicals and destroy the ozone layer.

Solvents that do not adversely affect the ozone layer are known as perfluorocarbon (hereinafter referred to as "PFC"), hydrofluorocarbon (hereinafter referred to as HFC), and hydrofluoroether (hereinafter referred to as HFE). However, HFC and PFC have a large global warming potential, so they are the target substances regulated by the Kyoto Protocol. In addition, HFC, HFE, and PFC are still a problem from the viewpoint of the low solubility of the above-mentioned nonvolatile compounds.

Solvents that do not have adverse effects on the global environment, are low in toxicity, and have excellent solubility for the above-mentioned non-volatile compounds are well known as trans-1,2-dichloroethylene (trans-CHCl=CHCl, also referred to as "tDCE" hereinafter) ). However, tDCE has a flash point, so it is difficult to use it alone.

In view of this, there are documents suggesting to combine tDCE and HFE with no flash point to prepare an azeotropic or azeotrope-like composition, and make it into a non-flammable solvent composition for cleaning purposes. For example, Patent Document 1 describes a combination of tDCE and 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (CF ₃ CH ₂ OCF ₂ CF ₂ H, the following also It is called "HFE-347pc-f") composed of azeotrope or azeotrope-like composition. In addition, Patent Document 2 describes a solvent composition containing an azeotropic or azeotrope-like composition composed of tDCE, HFE-347pc-f, methanol, ethanol, or 2-propanol. Prior Art Document Patent Document

Patent Document 1: Japanese Patent No. 2879847 Patent Document 2: Japanese Patent No. 4556669

SUMMARY OF THE INVENTION The problem to be solved by the invention The solvent composition described in Patent Document 1 and Patent Document 2 is an azeotrope-like composition, so even if it is used in a solvent cleaning device like repeated evaporation and condensation, the tDCE concentration will not change with the phase change. Change, the solvent composition can maintain non-flammability and can be used safely. However, as a result of adjusting the composition so as to become an azeotrope-like composition, the tDCE content of the composition of Patent Document 1 is 40-50% by mass, and the tDCE content of the composition of Patent Document 2 is only 61% by mass at the maximum. Increase tDCE content. As described above, HFE has lower solubility for non-volatile compounds such as processing oils and lubricants than tDCE, so the solvent composition described in Patent Document 1 and Patent Document 2 cannot obtain sufficiently high solubility.

In addition, if a high concentration of tDCE is contained in order to obtain high solubility to non-volatile compounds such as processing oils and lubricants, tDCE has a flash point, and therefore the solvent composition cannot be maintained incombustible.

The present invention was implemented to solve the above-mentioned problems, and its purpose is to provide a solvent composition containing tDCE that does not have an adverse effect on the global environment, has high solubility, is non-flammable, and is used even when used with phase change. A solvent composition that can maintain the initial non-combustibility; and a method for cleaning articles that uses the solvent composition to have high cleaning properties, does not have an adverse effect on the global environment, and can ensure safety.

Furthermore, the object of the present invention is to provide a composition for forming a coating film that uses a solvent composition containing tDCE, does not have volatile components adversely affecting the global environment during use, is non-flammable, and can form a homogeneous coating film, and A method of safely forming a homogeneous coating film using the composition for forming a coating film without adversely affecting the global environment. Means to solve the problem

The present invention provides a solvent composition, a cleaning method, a coating film forming composition, and a coating film forming method having the following constitutions [1] A solvent composition containing: trans-1,2-dichloroethylene (below Also known as "tDCE"), the first hydrofluoroether with a boiling point of 40~65°C (hereinafter also referred to as "HFE(A)"), and the second hydrofluoroether with a boiling point of 70~120°C (hereinafter also called "HFE (B)”); The aforementioned HFE(A) contains selected from 1,1-difluoroethyl-2,2,2-trifluoroethyl ether (hereinafter also referred to as "HFE-365mf-c"), 1 ,1,2,2-Tetrafluoroethyl-2,2,2-trifluoroethyl ether (hereinafter also referred to as "HFE-347pc-f") and 1,1-difluoroethyl-2,2,3 , 3,3-Pentafluoropropyl ether (hereinafter also referred to as "HFE-467sc-f") constitutes at least one of the group; relative to the total amount of tDCE, the aforementioned HFE(A) and the aforementioned HFE(B), The ratio of tDCE is 65~80% by mass, the ratio of the aforementioned HFE(A) is 5-25% by mass, and the ratio of the aforementioned HFE(B) is 5-25% by mass.

[2] The solvent composition as described in [1], wherein the aforementioned HFE (B) contains at least one selected from the group consisting of: ethoxynonafluorobutane (hereinafter also referred to as "HFE- 569s1''), 1,1,2,3,3,3-hexafluoropropyl-2,2,2-trifluoroethyl ether (hereinafter also referred to as "HFE-449mec-f"), 1,1,2 ,2-Tetrafluoroethyl-2,2,3,3,3-pentafluoropropyl ether (hereinafter also referred to as "HFE-449pc-f"), 1,1-difluoroethyl-2,2,3 ,3-Tetrafluoropropyl ether (hereinafter also referred to as "HFE-476pcf-c"), 1,1,2,3,3,3-hexafluoropropyl-2,2,3,3,3-pentafluoro Propyl ether (hereinafter also referred to as "HFE-54-11mec-f"), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (hereinafter also referred to as "HFE -458pc-fc''), 1,1,2,3,3,3-hexafluoropropyl-2,2,3,3-tetrafluoropropyl ether (hereinafter also referred to as "HFE-55-10mec-fc" ) And 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane (C ₂ F ₅ CF(OCH ₃ )CF (CF ₃ )CF ₃ , sometimes expressed by chemical formula below).

[3] The solvent composition as described in [1] or [2], wherein the aforementioned HFE (A) is HFE-347pc-f, and the aforementioned HFE (B) is HFE-569s1, compared to tDCE and HFE-347pc-f When combined with HFE-569s1, the ratio of tDCE is 65~80% by mass, the ratio of HFE-347pc-f is 5-25% by mass, and the ratio of HFE-569s1 is 5-25% by mass. [4] The solvent composition according to any one of [1] to [3], wherein the total ratio of tDCE, HFE(A) and HFE(B) is 90-100 relative to the total amount of the aforementioned solvent composition quality%.

[5] The solvent composition as described in any one of [1] to [4], which is used to clean the dirt of the article to be cleaned. [6] A washing method characterized by bringing the solvent composition as described in the aforementioned [5] into contact with the article to be washed. [7] A composition for forming a coating film, which contains the solvent composition described in any one of [1] to [4] and a non-volatile organic compound. [8] The composition for forming a coating film as described in [7], wherein the non-volatile organic compound is a lubricant. [9] The composition for forming a coating film as described in [8], wherein the lubricant is at least one selected from the group consisting of silicone lubricants and fluorine lubricants. [10] A method for forming a coating film, characterized in that the composition for forming a coating film as described in any one of [7] to [9] is applied to an object to be coated, and then the solvent is formed The substance evaporates to form a coating film composed of the aforementioned non-volatile organic compounds. Invention effect

According to the present invention, it is possible to provide a solvent composition containing tDCE that does not adversely affect the global environment, has high solubility, is non-flammable, and can maintain the initial non-flammability even when used with phase change Composition; and a method for cleaning articles that uses the solvent composition to have high cleaning properties, does not have an adverse effect on the global environment, and can ensure safety.

According to the present invention, it is possible to provide a composition for forming a coating film that uses a solvent composition containing tDCE, does not have a negative impact on the global environment when volatile components are used, is non-flammable, and can form a homogeneous coating film; and a composition for forming a homogeneous coating film; A method of safely forming a homogeneous coating film using the composition for forming a coating film under the adverse effects of the global environment.

Forms for implementing the invention The solvent composition of the present invention contains tDCE, HFE(A) with a boiling point of 40~65℃ and HFE(B) with a boiling point of 70~120℃; the aforementioned HFE(A) contains selected from HFE -At least one of the group consisting of 365mf-c, HFE-347pc-f and HFE-467sc-f; relative to the total amount of tDCE, HFE(A) and HFE(B), the ratio of tDCE is 65~80 mass %, the ratio of HFE(A) is 5-25% by mass, and the ratio of HFE(B) is 5-25% by mass.

In the present invention, by combining tDCE, HFE(A), and HFE(B) with the above ratios, respectively, a composition with high tDCE content and high solubility can be provided, and it is non-flammable, even in With the use of phase change, the tDCE concentration can still be maintained at the same level in the gas and liquid phases while maintaining the non-combustible composition. The components contained in the solvent composition of the present invention will be described below.

(tDCE) tDCE is an olefin with a double bond between carbon atom and carbon atom, so it has a short life in the atmosphere and will not have a negative impact on the global environment. The boiling point of tDCE is about 49°C, so it has good drying properties. In addition, even if it boils and turns into steam, it is about 49°C, so even parts that are susceptible to heat are not prone to adverse effects. The surface tension and viscosity of tDCE are low, and it is easy to evaporate at room temperature.

tDCE contains chlorine in the molecule, so it has very high solubility in processing oil and other organic substances, and can be used for degreasing cleaning, flux cleaning, precision cleaning, etc. of processing oil. The solubility of non-volatile organic compounds such as lubricants of tDCE is good. Therefore, it can be used as a solvent for coating film formation solutions that use the non-volatile organic compound as a solute. In addition, tDCE has a flash point.

In this specification, having a flash point means having a flash point between 23°C and the boiling point, and having no flash point means having no flash point between 23°C and the boiling point. In addition, non-combustibility means no flash point.

Commercial products of tDCE can be listed as follows. "Trans-LC (registered trademark)" (manufactured by Daido Air Products Electronics, Inc.). "Trans-1,2-dichloroethylene" (manufactured by AXIALL CORPORATION).

(HFE(A)) HFE(A) has a boiling point of 40~65°C and contains at least one selected from the group consisting of HFE-365mf-c, HFE-347pc-f, and HFE-467sc-f. HFE(A) may be used only 1 type or in combination of 2 or more types. HFE(A) is preferably at least one selected from the group consisting of HFE-365mf-c, HFE-347pc-f, and HFE-467sc-f.

HFE(A) is a hydrofluoroether with a boiling point in the range of 40~65℃. By including HFE(A) together with HFE(B) in the above ratio, when the solvent composition of the present invention is used in the cleaning device, tDCE The concentration is not easy to change. Furthermore, from the point of view that the concentration of tDCE is more difficult to change, the boiling point of HFE(A) is preferably 50~60°C, more preferably 54~58°C. Based on the above point of view, HFE-347pc-f is the best for HFE(A), and HFE-347pc-f alone is particularly preferred. In addition, in this specification, the boiling point refers to the normal boiling point at 1 atmosphere.

(HFE-347pc-f) The ozone destruction coefficient of HFE-347pc-f is zero, and the global warming potential is small. HFE-347pc-f has a boiling point of about 56°C, so it has good drying properties and is easy to evaporate at room temperature. Moreover, even if it is boiled and turned into steam, it is unlikely to have an adverse effect on parts that are susceptible to heat such as resin parts. HFE-347pc-f has no flash point. HFE-347pc-f has low surface tension and viscosity.

HFE-347pc-f has low solubility in non-volatile organic compounds such as processing oils and lubricants, but it still has the properties of being sufficient as a solvent for cleaning solvents or coating film forming solutions such as lubricants.

HFE-347pc-f can be manufactured by the following method, for example. A method of reacting 2,2,2-trifluoroethanol and tetrafluoroethylene in the presence of an aprotic polar solvent and catalyst (alkali metal alkoxide or alkali metal hydroxide) (refer to International Publication No. 2004/108644 number).

Commercial products of HFE-347pc-f can be listed as follows. "ASAHIKLIN (registered trademark) AE-3000" (manufactured by Asahi Glass Co., Ltd.).

(HFE-365mf-c) HFE-365mf-c has a zero ozone destruction coefficient and has a low global warming potential. HFE-365mf-c has a boiling point of about 40°C, so it has good drying properties and is easy to evaporate at room temperature. Moreover, even if it is boiled and turned into steam, it is unlikely to have an adverse effect on parts that are susceptible to heat such as resin parts. HFE-365mf-c has low surface tension and viscosity.

HFE-365mf-c can be manufactured by the following method, for example. A method of reacting 2,2,2-trifluoroethanol and difluoroethylene in the presence of an aprotic polar solvent and catalyst (alkali metal alkoxide or alkali metal hydroxide) (refer to Japanese Patent Application Publication No. 9- 263559).

(HFE-467sc-f) HFE-467sc-f has a zero ozone destruction coefficient and has a low global warming potential. HFE-467sc-f has a boiling point of about 59°C, so it has good drying properties and is easy to evaporate at room temperature. Moreover, even if it is boiled and turned into steam, it is unlikely to have an adverse effect on parts that are susceptible to heat such as resin parts. HFE-467sc-f has low surface tension and viscosity.

HFE-467sc-f can be manufactured by the following method, for example. A method of reacting 2,2,3,3,3-pentafluoropropanol and difluoroethylene in the presence of aprotic polar solvents and catalysts (alkali metal alkoxides or alkali metal hydroxides) (reference Japan Special Publication No. 9-263559).

(HFE(B)) HFE(B) is a compound with a boiling point of 70~120℃. Specific examples of HFE(B) include: HFE-569s1, HFE-449mec-f, HFE-449pc-f, HFE-476pcf-c, HFE-54-11mec-f, HFE-458pc-fc, HFE-55- 10mec-fc, C ₂ F ₅ CF(OCH ₃ )CF(CF ₃ )CF _3, etc. For HFE (B), only one of the above-mentioned compounds may be used or two or more of them may be used in combination.

HFE(B) is a hydrofluoroether with a boiling point in the range of 70~120℃. By including HFE(B) together with HFE(A) in the above ratio, when the solvent composition of the present invention is used in the cleaning device, tDCE The concentration is not easy to change. Furthermore, from the point of view that the concentration of tDCE is more difficult to change, HFE-569s1 is the best for HFE (B), and HFE-569s1 alone is particularly preferred.

(HFE-569s1) HFE-569s1 is selected from 1-ethoxy-2-trifluoromethyl-1,1,2,3,3,3-hexafluoropropane (C ₂ H ₅ OCF ₂ C(CF ₃ ) FCF ₃ ) and 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane (C ₂ H ₅ OCF ₂ CF ₂ CF ₂ CF ₃ ) Consists of more than one species. 1-ethoxy-2-trifluoromethyl-1,1,2,3,3,3-hexafluoropropane and 1-ethoxy-1,1,2,2,3,3,4,4 ,4-Nonafluorobutane are structural isomers of each other, and the properties of flammability, solubility, toxicity and burden on the global environment are all similar. Therefore, the properties of HFE-569s1 shown below are also applicable to 1-ethoxy-2-trifluoromethyl-1,1,2,3,3,3-hexafluoropropane, 1-ethoxy-1,1 ,2,2,3,3,4,4,4-nonafluorobutane and mixtures of the two in various ratios.

HFE-569s1 has a boiling point of about 76°C and no flash point. The ozone destruction coefficient of HFE-569s1 is zero, and the global warming potential is small.

The commercially available product of HFE-569s1, for example, can be "Novec (registered trademark) 7200" (manufactured by 3M Japan Co., Ltd.) (1-ethoxy-2-trifluoromethyl-1,1,2,3,3,3). -Hexafluoropropane and 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane in the composition range of 70:30~50:50 (mass ratio) Mixture) to start.

HFE-569s1 can be manufactured by a known method. For example, according to the method of Japanese Patent No. 3068199, CF ₃ CF ₂ CF ₂ C(O)F, CF ₃ CF(CF ₃ )C(O)F and C ₂ F ₅ C(O)CF ₃ and the An arbitrary and appropriate supply source of anhydrous fluoride ions such as a mixture of anhydrous alkali metal fluoride (such as potassium fluoride or cesium fluoride) or anhydrous silver fluoride, etc., in a quaternary ammonium compound (such as "ADOGEN (registered trademark) 464" (manufactured by Aldrich Chemical Company)) is prepared by reacting with an alkylating agent such as diethyl sulfate in an anhydrous polar aprotic solvent.

(HFE-449mec-f) HFE-449mec-f has a zero ozone destruction coefficient and has a low global warming potential. The boiling point of HFE-449mec-f is 72°C. HFE-449mec-f can be manufactured, for example, by the following method. A method of reacting 2,2,2-trifluoroethanol and hexafluoropropylene in the presence of an aprotic polar solvent and catalyst (alkali metal alkoxide or alkali metal hydroxide) (refer to Japanese Patent Application Publication No. 9-263559 number).

(HFE-449pc-f) The ozone destruction coefficient of HFE-449pc-f is zero, and the global warming potential is small. The boiling point of HFE-449pc-f is 73°C. HFE-449pc-f can be manufactured, for example, by the following method. A method of reacting 2,2,3,3,3-pentafluoropropanol with tetrafluoroethylene in the presence of aprotic polar solvents and catalysts (alkali metal alkoxides or alkali metal hydroxides) (refer to Japan Special Publication No. 9-263559).

(HFE-476pcf-c) The ozone destruction coefficient of HFE-476pcf-c is zero, and the global warming potential is small. The boiling point of HFE-476pcf-c is 85°C. HFE-476pcf-c can be manufactured by the following method, for example. A method of reacting 2,2,3,3-tetrafluoropropanol and difluoroethylene in the presence of aprotic polar solvents and catalysts (alkali metal alkoxides or alkali metal hydroxides) (refer to Japanese special Kaiping No. 9-263559).

(HFE-54-11mec-f) The ozone destruction coefficient of HFE-54-11mec-f is zero, and the global warming potential is small. The boiling point of HFE-54-11mec-f is 86°C. HFE-54-11mec-f can be manufactured by the following method, for example. A method of reflecting 2,2,3,3,3-pentafluoropropanol and hexafluoropropene in the presence of aprotic polar solvents and catalysts (alkali metal alkoxides or alkali metal hydroxides) (reference Japan Special Publication No. 9-263559).

(HFE-458pc-fc) HFE-458pc-fc has a zero ozone destruction coefficient and has a low global warming potential. The boiling point of HFE-458pc-fc is 95°C. HFE-458pc-fc can be manufactured, for example, by the following method. A method of reacting 2,2,3,3-tetrafluoropropanol with tetrafluoroethylene in the presence of aprotic polar solvents and catalysts (alkali metal alkoxides or alkali metal hydroxides) (refer to Japanese Patent Application Publication 9-263559).

(HFE-55-10mec-fc) The ozone destruction coefficient of HFE-55-10mec-fc is zero, and the global warming potential is small. The boiling point of HFE-55-10mec-fc is 102°C. HFE-55-10mec-fc can be manufactured, for example, by the following method. A method of reacting 2,2,3,3-tetrafluoropropanol and hexafluoropropene in the presence of aprotic polar solvents and catalysts (alkali metal alkoxides or alkali metal hydroxides) (refer to Japanese Patent Application Publication 9-263559).

(C ₂ F ₅ CF(OCH ₃ )CF(CF ₃ )CF ₃ ) C ₂ F ₅ CF(OCH ₃ )CF(CF ₃ )CF _{3 has} an ozone destruction coefficient of zero and a low global warming potential. The boiling point of C ₂ F ₅ CF(OCH ₃ )CF(CF ₃ )CF ₃ is 98°C. C ₂ F ₅ CF(OCH ₃ )CF(CF ₃ )CF ₃ can be manufactured by a known method. For example, it can be manufactured by the following method.

CF ₃ -(CF ₂ ) _n -C(O)R ^{f can be} used as a raw material to make an arbitrary and well-known supply source of anhydrous alkali metal fluoride (such as potassium fluoride or cesium fluoride) or anhydrous fluoride ion such as silver fluoride , It is prepared by reacting with an alkylating agent such as diethyl sulfate in an anhydrous polar aprotic solvent in the presence of a quaternary ammonium compound. (Refer to German Patent No. 1294949).

C ₂ F ₅ CF(OCH ₃ )CF(CF ₃ )CF ₃ can be obtained, for example, from commercially available products such as "Novec (registered trademark) 7300" (manufactured by 3M Japan Co., Ltd.).

(Composition of solvent composition) For the solvent composition of the present invention, relative to the total amount of tDCE, HFE(A) and HFE(B), the ratio of tDCE is 65~80% by mass, and the ratio of HFE(A) is 5-25% by mass, the ratio of HFE(B) is 5-25% by mass.

For the solvent composition of the present invention, for example, when only HFE-347pc-f is used for HFE(A) and only HFE-569s1 is used for HFE(B), compared to the total of tDCE, HFE-347pc-f and HFE-569s1 The ratio of tDCE is 65~80% by mass, the ratio of HFE-347pc-f is 5-25% by mass, and the ratio of HFE-569s1 is 5-25% by mass.

The solvent composition of the present invention contains tDCE and HFE (A) and HFE (B) within the above-mentioned composition range, so as to solve the problem that tDCE and HFE-347pc-f contained tDCE at a high concentration in the past. It is impossible to maintain the non-combustibility under the use with phase change.

In a two-component composition of tDCE and a HFE(A) such as HFE-347pc-f, once the tDCE content exceeds the range of azeotrope-like composition, it is non-flammable at the initial stage even when used with phase change Composition, tDCE will also be concentrated into a liquid phase during evaporation and become a flammable composition (hereinafter also referred to as "flammable composition"). Therefore, in the past, an azeotrope-like composition that hardly changes the composition of the composition due to a phase change was used to suppress the increase in the concentration of tDCE. However, an azeotrope-like composition composed of tDCE and HFE-347pc-f The tDCE content is not high.

On the other hand, compared to the conventional azeotrope-like composition containing tDCE and one type of HFE(A), such as HFE-347pc-f, the solvent composition of the present invention has a higher tDCE content and is used in conjunction with phase change. At least in the gas phase and the liquid phase, the tDCE content is almost unchanged. This is believed to be because HFE(B) added to tDCE and HFE(A) at a predetermined ratio has the effect of promoting the volatilization of tDCE from the liquid phase to the gas phase during evaporation, preventing tDCE from condensing into a liquid phase and suppressing changes in tDCE content. To. Due to this effect, the solvent composition of the present invention can suppress fluctuations in tDCE content, such as in a washing device that repeatedly evaporates and condenses, and therefore can maintain non-combustibility. In addition, when the solvent composition of the present invention is put into a pure washing tank for use, it is also possible to suppress the volatilization of the solvent composition and condensing tDCE into a liquid phase to become a flammable composition.

With respect to the solvent composition of the present invention, the ratio of tDCE is 65 to 80% by mass relative to the total amount of tDCE, HFE (A), and HFE (B). Hereinafter, the "tDCE ratio" means the ratio of tDCE to the total amount of tDCE, HFE(A), and HFE(B). The same applies to "HFE(A) ratio" and "HFE(B) ratio".

If the tDCE ratio is less than 65% by mass, the solubility with non-volatile organic compounds, especially mineral oil, which is the main component of processed oil, cannot be sufficiently obtained. At this time, it will be the cause of poor cleaning for cleaning purposes. For example, after cleaning, the processing oil remains on the article to be cleaned, or the processing oil mixed in by the cleaning does not dissolve in the solvent composition, so the solvent When the composition becomes white turbid or two-layer separation occurs and the article to be washed is continuously processed, the article to be washed will be secondly contaminated, etc. In addition, once the tDCE ratio exceeds 80% by mass, the solvent composition is likely to become flammable when used with phase change, and it is difficult to form a coating film for cleaning purposes or when using a coating film formation composition to form a coating film. Maintain non-combustibility.

In the solvent composition of the present invention, the HFE (A) ratio is 5-25% by mass. If the HFE(A) ratio is less than 5% by mass, the incombustibility of the solvent composition is likely to be lost when the solvent composition is used with phase change. In addition, if the HFE(A) ratio exceeds 25% by mass, the solubility of processing oils, lubricants, etc., necessary as a solvent for cleaning or as a composition solvent for coating film formation, will decrease.

In the solvent composition of the present invention, the HFE (B) ratio is 5-25% by mass. If the HFE(B) ratio is less than 5 mass%, HFE(B) cannot fully promote the volatilization of tDCE under the use of a solvent composition with phase change, and it is easy to lose the incombustibility of the solvent composition. In addition, if the HFE(B) ratio exceeds 25% by mass, the solubility of processing oils, lubricants, etc., necessary as a solvent for cleaning or as a composition solvent for coating film formation, will decrease.

In addition, based on, for example, the vapor tank and washing tank of a washing device that repeatedly performs evaporation and condensation as shown in Figure 1 described later, the tDCE content of the solvent composition falls within a non-flammable composition (hereinafter referred to as "non-flammable When the solvent composition is volatilized or used as a composition for coating film formation in a simple washing container without distillation and regeneration function, even if the tDCE content of the solvent composition is high, the fluctuation of tDCE content can be sufficiently suppressed. From other viewpoints, the solvent composition of the present invention has a tDCE ratio of 65 to 78% by mass, a HFE(A) ratio of 5 to 20% by mass, and a HFE(B) ratio of 10 to 25% by mass. Preferably, the ratio is 67 to 75% by mass, the HFE (A) ratio is 5 to 15% by mass, and the HFE (B) ratio is 15 to 25% by mass.

Relative to the total amount of the solvent composition, the total content of tDCE, HFE(A) and HFE(B) in the solvent composition of the present invention is preferably 90-100% by mass, preferably 95-100% by mass, and particularly preferably 100% by mass .

In addition to tDCE, HFE(A) and HFE(B), the solvent composition of the present invention may contain other solvents other than tDCE, HFE(A) and HFE(B) within a range that does not impair the effects of the present invention (only below Called "other solvents"), it can also contain various additives other than solvents.

Other solvents are preferably organic solvents that are soluble in tDCE and have no flash point, and can be selected appropriately for various purposes such as improving solubility and adjusting the volatilization rate. Other solvents include tDCE-soluble hydrocarbons, alcohols, ketones, ethers, esters, chlorocarbons (except tDCE), HFC, HFE (except HFE(A) and HFE(B)), hydrofluoroolefins (hereinafter referred to as ``HFO "), chlorofluoroolefins (hereinafter referred to as "CFO"), hydrochlorofluoroolefins (hereinafter referred to as "HCFO"), etc. The other solvents may be one type or two or more types.

Relative to the total amount of the solvent composition, the content of other solvents in the solvent composition of the present invention is preferably 0-10% by mass, preferably 0-5% by mass. The solvent composition of the present invention achieves both high solubility and maintaining non-combustibility under use with phase change at the above-mentioned content ratios of tDCE, HFE-347pc-f and HFE-569s1, so it is particularly preferred that it does not contain other solvents.

Various additives other than the solvent of the solvent composition of the present invention include stabilizers, metal corrosion inhibitors, and the like. Specific examples of stabilizers include: nitromethane, nitroethane, nitropropane, nitrobenzene, diethylamine, triethylamine, isopropylamine, diisopropylamine, butylamine, isobutylamine, tertiary butylamine, α-methyl Pyridine, N-methylbenzylamine, diallylamine, N-methylmorphine, phenol, o-cresol, m-cresol, p-cresol, revanol, p-butyl phenol, tertiary butyl catechin Phenol, catechol, isoeugenol, o-methoxyphenol, 4,4'-dihydroxyphenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, 2,6-Di-tertiary butyl-p-cresol, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tertiary butyl -5'-methylphenyl)-5-chlorobenzotriazole, 1,2,3-benzotriazole, 1-[(N,N-bis-2-ethylhexyl)aminomethyl] Benzotriazole, 1,2-propylene oxide, 1,2-butylene oxide, 1,4-dioxane, butyl glycidyl ether, phenyl glycidyl ether, etc. The stabilizer may be one type or two or more types.

Relative to the total amount of the solvent composition, the content of various additives other than the solvent in the solvent composition of the present invention is preferably 0 to 5% by mass, preferably 0 to 1% by mass. Relative to the total amount of the solvent composition, the total content of other solvents and various additives is preferably 10% by mass or less, preferably 1% by mass or less, and more preferably not containing.

The solvent composition of the present invention is a solvent composition that does not adversely affect the global environment, has high solubility to non-volatile organic compounds such as processing oil, is non-flammable, and can maintain the initial non-flammability even when used with phase change It is suitable for cleaning purposes such as degreasing cleaning, flux cleaning, precision cleaning, and dry cleaning. In addition, the solvent composition of the present invention can also be used to dissolve the following solvents to form a coating film forming composition, and apply it on the surface of an article to form a coating film: lubricants such as silicone lubricants, fluorine lubricants, etc. Anti-corrosion agent composed of mineral oil or synthetic oil, moisture-proof coating agent for water repellent treatment, anti-fouling coating agent for anti-fouling treatment, anti-fingerprint adhesion agent, etc.

The articles to which the solvent composition of the present invention can be applied can be widely used in electronic parts such as capacitors, diodes, transistors, SAW filters, etc., which constitute the basic components of electronic circuits, as well as substrates or equipment, lenses and Optical parts such as polarizers, auto parts such as fuel injection needles and drive gears used in automobile engines, mechanical parts such as drive parts and exterior parts used in industrial automatic machines, and machine tools such as cutting tools The super hard tools and so on. In addition, the materials that can be applied to the solvent composition of the present invention can include a wide range of materials such as metals, plastics, elastomers, glass, ceramics, cloth, etc. Among them, iron, copper, nickel, gold, silver, platinum, etc. Engineering plastics such as metal, sintered metal, glass, fluororesin, PEEK, etc. are suitable.

[Washing method] The washing method of the present invention is a method of using the above-mentioned solvent composition of the present invention to clean the adherents attached to the article to be cleaned, and is characterized in that the solvent composition of the present invention is cleaned with Item contact.

In the cleaning method of the present invention, the attachments to be cleaned and removed can include various fluxes, cutting oils, quenching oils, rolling oils, lubricating oils, machine oils, pressing oils, and punching materials attached to the articles to be cleaned. Processing oil such as hole oil, drawing oil, assembly oil, and drawing oil, mold release agent, dust, etc. Compared with the conventional solvent composition HFC or HFE, the solvent composition has better solubility for processing oil, so it is suitable for cleaning processing oil.

In addition, the solvent composition of the present invention has a high cleaning power, which is one of its characteristics. It can remove the asphalt component called pitch that cannot be removed by conventional cleaning agents HCFCs, so it can not only clean general metalworking oils. , Also suitable for removing asphalt components. For example, it is suitable for removing asphalt components used for surface protection materials during glass processing.

In addition, the solvent composition of the present invention can be used to clean articles to be cleaned of various materials such as metals, plastics, elastomers, glass, ceramics, and composite materials thereof. In addition, the solvent composition of the present invention can be used for cleaning various clothing stains composed of cloth made of natural fiber or synthetic fiber.

The cleaning method of the article to be cleaned using the solvent composition of the present invention is not particularly limited except that the solvent composition of the present invention is brought into contact with the article to be cleaned. For example, hand washing, immersion washing, spray washing, immersion shaking washing, immersion ultrasonic washing, steam washing, and a combination of these methods may be used. The cleaning conditions and cleaning device such as the time and frequency of the aforementioned contact and the temperature of the solvent composition of the present invention can be appropriately selected.

For the cleaning method of the present invention, a cleaning method having the following steps is suitable: a solvent contact step, contacting the article to be cleaned with the solvent composition of the present invention in the liquid phase; and a vapor contact step, after the solvent contact step Expose the aforementioned items to be cleaned to steam, which evaporates a non-flammable solvent composition (hereinafter referred to as "solvent composition (V)") containing tDCE, HFE (A) and HFE (B) to generate vapor And produced.

The solvent composition (V) and the solvent composition of the present invention can be made the same except that the ratio range of tDCE, HFE(A), HFE(B) to the total amount of tDCE, HFE(A) and HFE(B) is different. The solvent composition. The ratios of tDCE, HFE (A), and HFE (B) of the solvent composition (V) to the total amount of tDCE, HFE (A) and HFE (B) are 65 to 80% by mass, 5 to 25% by mass, and 5, respectively. ~25% by mass is better. As long as it is within this range, it can be a composition with a high tDCE content and high solubility, and the tDCE concentration in the gas phase and the liquid phase will be the same under use with phase change, and the non-combustibility can be maintained.

Fig. 1 schematically shows an example of a cleaning device for performing the cleaning method of the present invention having the above-mentioned solvent contact step and vapor contact step. Hereinafter, the above-mentioned washing method will be explained by taking the case of using the washing device shown in FIG. 1 as an example.

The cleaning device 10 shown in FIG. 1 is a 3-tank ultrasonic cleaning device mainly used for cleaning electronic and electrical parts, precision mechanical parts, optical machine parts, etc. The cleaning device 10 has a cleaning tank 1, a rinsing tank 2, and a steam generating tank 3 containing solvent compositions La, Lb, and Lc, respectively. The cleaning device 10 is further provided with a vapor zone 4 filled with vapor generated by the solvent composition La, Lb, and Lc above the tanks; a cooling pipe 9 for cooling the vapor; and a water separation tank 5, the water separation tank The system 5 is used to statically separate the solvent composition Lm condensed through the cooling pipe 9 from the water adhering to the cooling pipe. In actual washing, the article D to be washed is placed in a special jig or cage, etc., in the washing device 10 along the solvent composition La contained in the washing tank 1 and the solvent composition contained in the washing tank 2 In Lb, the steam area 43 directly above the steam generating tank 3 moves in order to complete the cleaning.

In this type of cleaning device, the solvent composition of the present invention can be used at least as the solvent composition La contained in the cleaning tank 1 and the solvent composition Lb contained in the rinse tank 2. The solvent composition Lc contained in the vapor generating tank 3 is the solvent composition (V), but the solvent composition of the present invention is preferred.

A heater 7 and an ultrasonic vibrator 8 are provided in the lower part of the washing tank 1. In the washing tank 1, the solvent composition La is heated by the heater 7 and controlled at a constant temperature. At the same time, the cavitation generated by the ultrasonic vibrator 8 is used to impart physical external force to the article D to be cleaned. Washing removes dirt adhering to the article D to be washed. At this time, in addition to ultrasonic waves, physical external forces can also use various methods currently used in washing machines, such as shaking or jet flow of the solvent composition La in the liquid. In addition, when washing the article D to be washed in the washing tank 1, ultrasonic vibration is not necessary, and washing without ultrasonic vibration can be performed on demand. In addition, the temperature of the solvent composition La in the washing tank 1 is preferably 25° C. or higher and lower than the boiling point of the solvent composition a. As long as it is within the above range, degreasing and cleaning such as processing oil can be easily performed, and the cleaning effect by ultrasonic waves is high.

In the washing device 10, when the article D to be washed is moved from the washing tank 1 to the rinsing tank 2, the solvent composition La component has already adhered to the surface to be washed. Therefore, it is possible to prevent the dirt on the surface of the cleaned article D from being fixed due to drying while moving the cleaned article D to the rinsing tank 2.

In the rinsing tank 2, the article D to be cleaned is immersed in the solvent composition Lb, and the dirt components adhering to the article D to be cleaned are removed in a state of being dissolved in the solvent composition La. The rinsing tank 2 may also have a mechanism that can impart a physical external force to the article D to be washed as in the washing tank 1. The washing device 10 is designed so that the overflow of the solvent composition Lb contained in the washing tank 2 flows into the washing tank 1. Moreover, the washing tank 1 is equipped with the piping 11 which conveys the solvent composition La to the vapor generation tank 3, and prevents the liquid level from exceeding a predetermined height.

A heater 6 for heating the solvent composition Lc in the steam generating tank 3 is installed at the lower part of the steam generating tank 3. After the solvent composition Lc contained in the steam generating tank 3 is heated and boiled by the heater 6, part or all of its composition becomes vapor and rises upward as indicated by the arrow 13 to form a vapor zone full of steam V directly above the steam generating tank 3 43. The article D to be washed after finishing washing in the rinsing tank 2 is moved to the steam zone 43 and exposed to the steam V for steam washing (steam contact step). In the steam cleaning, the object D to be cleaned is cleaned with the components of the steam V condensed on the surface of the object D to be cleaned and liquefied. The steam V contains no dirt components at all, so it is quite effective as the final cleaning at the end of the cleaning step. In addition, the vapor V is not necessarily formed only by vapor generated from the solvent composition Lc, and these aspects are also included in the vapor contact step in the cleaning method of the present invention.

In addition, the spaces above the tanks of the cleaning device 10 are all commonly used as the steam zone 4. The steam generated from the washing tank 1, the rinsing tank 2 and the steam generating tank 3 is cooled and condensed by the cooling pipe 9 installed at the upper part of the wall surface of the washing device 10, and is recovered from the steam zone 4 as the solvent composition Lm. The agglomerated solvent composition Lm is then stored in the water separation tank 5 through the pipe 14 connecting the cooling pipe 9 and the water separation tank 5. The water mixed with the solvent composition Lm in the water separation tank 5 is separated. The water-separated solvent composition Lm returns to the rinsing tank 2 through the pipe 12 connecting the water separation tank 5 and the rinsing tank 2. The cleaning device 10 can suppress the evaporation loss of the solvent composition by such a mechanism.

In addition, in order to improve the cleaning effect, a cooling device is provided in the rinsing tank 2, thereby keeping the temperature of the solvent composition Lb in the rinsing tank 2 at a low temperature, and by reducing the temperature of the cleaned article D to be immersed in advance, it is enlarged The difference between the temperature and the temperature of the steam can effectively increase the amount of condensation of the steam V on the surface of the article D to be cleaned. Specifically, the temperature of the solvent composition Lb in the rinsing tank 2 is preferably set to 10~45°C. In addition, from the viewpoint of detergency, the temperature of the solvent composition La in the washing tank 1 is preferably higher than the temperature of the solvent composition Lb in the rinsing tank 2.

In the washing device 10, the solvent composition La, Lb, and Lc contained in each tank is circulated in a liquid or gas intermittent state change, so that the dirt components carried into the washing tank 2 can be continuously accumulated in In the steam generating tank 3, the cleanliness of the rinsing tank 2 can be maintained and steam cleaning is performed in the steam zone 43.

When the washing device 10 is used in this embodiment to wash the articles to be washed, for example, the solvent composition of the present invention is put into the washing tank 1, the rinse tank 2 and the steam generating tank 3 at the start of operation as the solvent composition La , Lb, Lc, when the washing reaches a stable state, the solvent composition La and the solvent composition Lb can maintain the composition range of the solvent composition of the present invention, and the solvent composition Lc can become the composition of the solvent composition (V) range.

That is, in the case where the solvent composition of the present invention is the solvent composition L in the above-mentioned cleaning method, the solvent composition L that is input when the cleaning device 10 starts to operate will be in each case as the cleaning device 10 operates. The composition of the washing tank 1, the rinsing tank 2, the steam generating tank 3, the steam zone 4, and the water separation tank 5 is changed and stabilized. Although the composition of the solvent composition La and Lb contained in the stabilized washing tank 1 and the rinsing tank 2 is slightly changed compared with the solvent composition L, the composition is still highly soluble and incombustible. Within the scope of the solvent composition of the invention. The solvent composition Lc contained in the vapor generating tank 3 and the solvent composition L have a different composition in comparison with each other, and may fall outside the scope of the solvent composition of the present invention. Even in this case, the content ratio of tDCE is still low, and it is still within the composition range of the solvent composition (V), maintaining a non-flammable composition. Then, it stabilizes in this stable state, and continues to operate while ensuring high cleaning power and safety.

In addition, the cleaning method having the solvent contact step and the vapor contact step in the cleaning method of the present invention is not limited to the above-mentioned embodiment, and the present embodiment can be changed or modified without departing from the spirit and scope of the present invention. For example, the solvent contact step can be performed only once, but it should be repeated more than two times, and it is better to be repeated two to three times. In addition, the tank for collecting the condensed liquid obtained by condensing the vapor in the vapor zone may be a tank other than the rinse tank 2, and the condensed liquid may not be reused.

By using the solvent composition of the present invention, as far as the cleaning method of the present invention is concerned, it has high cleaning properties, does not have an adverse effect on the global environment, and can ensure safety even when used with phase change. Washing method. In addition, the articles cleaned by the solvent composition of the present invention have the characteristics that no residues such as processing oil are visible on the surface, and the surface condition after washing is good, so that washing defects are unlikely to occur.

[The composition for forming a coating film and the method for forming a coating film] The solvent composition of the present invention can be used as a solvent for dilute coating of non-volatile organic compounds. That is, the composition for forming a coating film of the present invention is characterized by containing the solvent composition of the present invention and a non-volatile organic compound. In addition, the method for forming a coating film of the present invention is characterized in that, after coating the composition for forming a coating film on the object to be coated, the solvent composition is evaporated to form a coating composed of the nonvolatile organic compound. membrane.

Here, the non-volatile organic compound of the present invention refers to a compound having a higher boiling point than the solvent composition of the present invention and the organic compound still remains on the surface after the solvent composition is evaporated. Specific examples of non-volatile organic compounds include: lubricants used to impart lubricity to articles, rust inhibitors used to impart rust prevention effects to metal parts, moisture-proof coating agents used to impart water repellency to articles, Anti-fouling coating agent such as anti-fingerprint adhesion agent for the anti-fouling performance of the article. Regarding the coating film forming composition and the coating film forming method of the present invention, it is preferable to use a lubricant for the nonvolatile organic compound from the viewpoint of solubility.

Lubricant refers to the thing that is used to reduce the friction of the contact surface to prevent heat generation or abrasion damage when the two components are in contact with each other. The lubricant can be in any form of liquid (oil), semi-solid (grease), and solid.

From the viewpoint of high solubility in tDCE, the lubricant is preferably a fluorine-based lubricant or a silicone-based lubricant. In addition, the fluorine-based lubricant refers to a lubricant having a fluorine atom in the molecule. In addition, silicone-based lubricants refer to lubricants containing silicone.

The lubricant contained in the composition for forming a coating film may be one type or two or more types. The fluorine-based lubricant and the silicone-based lubricant may be used alone or in combination.

Examples of the fluorine-based lubricant include fluorine-based solid lubricants such as fluorine oil, fluorine grease, and polytetrafluoroethylene resin powder. The fluorine oil is preferably a low polymer of perfluoropolyether and chlorotrifluoroethylene. Commercial products of fluorine oil include: product name "Krytox (registered trademark) GPL102" (manufactured by DuPont Co., Ltd.), "DAIFLOIL #1", "DAIFLOIL #3", "DAIFLOIL #10", "DAIFLOIL #20 ", "DAIFLOIL #50", "DAIFLOIL #100", "Demnum S-65" (above made by DAIKIN INDUSTRIES, LTD.), etc.

Fluorine grease is preferably made by blending fluorine oil such as perfluoropolyether or low polymer of chlorotrifluoroethylene as base oil with polytetrafluoroethylene powder or other thickening agents. Commercially available fluorine-based greases include the product names "Krytox (registered trademark) Grease 240AC" (manufactured by DuPont Co., Ltd.), "DAIFLOIL Grease DG-203", "Demnum L65", and "Demnum L100" , "Demnum L200" (manufactured by DAIKIN INDUSTRIES, LTD. above), "Sumitec F936" (manufactured by Sumitomo Lubricant Co., Ltd.), "Molykote (registered trademark) HP-300", "Molykote (registered trademark) HP-500 ", "Molykote (registered trademark) HP-870", "Molykote (registered trademark) 6169" (manufactured by Dow Corning Toray Co., Ltd. above), etc.

Silicone-based lubricants can include silicone oil or silicone grease. Polysiloxane oil is made of dimethyl polysiloxane, methyl hydrogen polysiloxane, methyl phenyl polysiloxane, cyclic dimethyl polysiloxane, amine modified polysiloxane, and diamine modified polysiloxane. Silicone, modified polysiloxane oil with organic groups introduced into the side chain or end is suitable. Examples of commercially available silicone oils include: "Shin-Etsu Silicone KF-96", "Shin-Etsu Silicone KF-965", "Shin-Etsu Silicone KF-968", "Shin-Etsu Silicone KF-99", "Shin-Etsu Silicone KF" -50", "Shin-Etsu Silicone KF-54", "Shin-Etsu Silicone HIVAC F-4", "Shin-Etsu Silicone HIVAC F-5", "Shin-Etsu Silicone KF-56A", "Shin-Etsu Silicone KF-995", "Shin-Etsu Silicone KF" -868", "Shin-Etsu Silicone KF-859" (manufactured by Shin-Etsu Chemical Co., Ltd. above), "SH200" (manufactured by Dow Corning Toray Co., Ltd.), etc.

The silicone grease is preferably a product that uses the various silicone oils listed above as the base oil, and blends thickeners such as metal soaps, and various additives. Examples of commercially available silicone greases include: product names "Shin-Etsu Silicone G-30 Series", "Shin-Etsu Silicone G-40 Series", "Shin-Etsu Silicone FG-720 Series", "Shin-Etsu Silicone G-411", "Shin-Etsu Silicone G-501", "Shin-Etsu Silicone G-6500", "Shin-Etsu Silicone G-330", "Shin-Etsu Silicone G-340", "Shin-Etsu Silicone G-350", "Shin-Etsu Silicone G-630" (Shin-Etsu Silicone G-630 above Chemical Industry Co., Ltd.), "Molykote (registered trademark) SH33L", "Molykote (registered trademark) 41", "Molykote (registered trademark) 44", "Molykote (registered trademark) 822M", "Molykote (registered trademark) 111", "Molykote (registered trademark) grease for high vacuum", "Molykote (registered trademark) thermal diffusion compound" (manufactured by Dow Corning Toray Co., Ltd. above), etc.

In addition, examples of fluorine-based lubricants and silicone-based lubricants include fluoropolysiloxane oils of modified silicone oils whose ends or side chains are substituted with fluoroalkyl groups. Examples of commercially available fluoropolysiloxane oils include: "Unidyne (registered trademark) TG-5601" (manufactured by DAIKIN INDUSTRIES, LTD.), "Molykote (registered trademark) 3451", "Molykote (registered trademark) 3452" "(Above Dow Corning Toray Co., Ltd.), "Shin-Etsu Silicone FL-5", "Shin-Etsu Silicone X-22-821", "Shin-Etsu Silicone X-22-822", "Shin-Etsu Silicone FL-100" ( The above Shin-Etsu Chemical Industry Co., Ltd.), etc.

These lubricants can be used as a coating film for industrial equipment, personal computers and audio equipment CD or DVD tray parts, printers, copying machines, flux machines, etc., which are usually used as coating films with fluorine-based lubricants. Machines or office machines, etc. For example, it can be used for injection needles or syringes, medical tubings, metal knives, catheters, etc., of syringes that are usually coated with silicone lubricants.

Anti-rust agent refers to the thing that covers the metal surface that is prone to rust due to the oxidation of oxygen in the air, and blocks the metal surface and oxygen to prevent the metal material from rusting. Rust inhibitors can include mineral oils or synthetic oils such as polyol esters, polyalkylene glycols, and polyvinyl ethers.

The moisture-proof coating agent or anti-fouling coating agent is used to impart moisture-proof or anti-fouling properties to plastic, rubber, metal, glass, and mounted circuit boards. Product examples of moisture-proof coating agents include: TOPAS 5013, TOPAS 6013, TOPAS 8007 (manufactured by Polyplastics Co., Ltd.), ZEONOR 1020R, ZEONOR 1060R (manufactured by Zeon Corporation), Apel 6011T, Apel 8008T (Mitsui Chemicals) Company system), SFE-DP02H, SNF-DP20H (manufactured by AGC SEIMI CHEMICAL CO., LTD.). Examples of antifouling coating agents such as anti-fingerprint adhesives include: Optool DSX, Optool DAC (manufactured by DAIKIN INDUSTRIES, LTD.), FLUOROSURF FG-5000 (manufactured by Fluoro Technology), and SR-4000A (AGC SEIMI CHEMICAL CO. , LTD.) and so on.

The composition for forming a coating film of the present invention is usually prepared with a solution composition in which a non-volatile organic compound is dissolved in the solvent composition of the present invention. The method for producing the composition for forming a coating film is not particularly limited as long as it can uniformly dissolve the non-volatile organic compound in the solvent composition of the present invention at a predetermined ratio. The composition for forming a coating film of the present invention is basically composed of only a non-volatile organic compound and the solvent composition of the present invention. In the following description, the composition for forming a coating film using a lubricant as a non-volatile organic compound is referred to as "lubricant solution". The same applies to the coating film forming composition using other non-volatile organic compounds.

Relative to the total amount of the lubricant solution (100% by mass), the lubricant content is preferably 0.01-50% by mass, preferably 0.05-30% by mass, and more preferably 0.1-20% by mass. The remainder of the lubricant solution excluding the lubricant is the solvent composition. As long as the lubricant content is within the above range, the film thickness of the coating film when the lubricant solution is applied and the thickness of the lubricant coating film after drying can be easily adjusted within an appropriate range.

In the coating film forming composition such as rust inhibitor solution, moisture-proof coating agent solution, and anti-fouling coating agent solution, rust-preventive agent, moisture-proof coating agent, moisture-proof coating agent, etc. are relatively non-volatile The content of the total amount of the organic compound solution (composition for coating film formation) is also preferably within the same range as the content of the lubricant in the aforementioned lubricant solution.

After coating the composition for forming a coating film containing the above-mentioned solvent composition and a nonvolatile organic compound on an object to be coated, the composition for forming a coating film by self-coating the solvent composition on the object to be coated Evaporation can form a coating film made of non-volatile organic compounds on the coated object.

Metals can be used to form coating films that can form lubricants, rust inhibitors, moisture-proof coating agents, anti-fouling coating agents, etc., that is, coatings that can be coated with coating film forming compositions containing these substances. , Plastics, elastomers, glass, ceramics and other materials to be coated. Specific items can include the items described in the non-volatile organic compounds above.

The coating method of the coating film forming composition may include: coating with bristles, coating with spray, coating by immersing the article in the coating film forming composition, and sucking the coating film forming composition to make Coating method in which the coating film forming composition contacts the inner wall of the tube or injection needle.

As a method of evaporating the solvent composition from the coating film forming composition, a known drying method can be mentioned. The drying method can be, for example, air drying, drying by heating, etc. The drying temperature should be 20~100℃.

The composition for forming a coating film of the present invention and the method of forming a coating film using it described above use the solvent composition of the present invention as a diluting coating solvent for non-volatile organic compounds, so it will not cause any harm to the global environment influences. In addition, the solvent composition of the present invention has a high tDCE content, so the solubility of non-volatile organic compounds is good, and there is no white turbidity or separation of non-volatile organic compounds during storage, and a uniform coating film can be formed. In addition, the solvent composition of the present invention does not form a composition with a flash point as the gas-liquid phase changes, so it is quite safe even if it is used to form a coating film. Example

The following examples illustrate the present invention in detail. The present invention is not limited by these embodiments. Examples 1 to 7, 11 to 17, 18 to 24, 27 to 29, and 30 to 36 are examples, and examples 8 to 10, 25, and 26 are comparative examples.

[Examples 1 to 17; Solvent composition] The following commercially available products tDCE, HFE-347pc-f, and HFE-569s1 were mixed in the ratio shown in Table 1 to prepare the solvent compositions of Examples 1 to 10.

(Manufacturer and product name of the compound) tDCE; trans-1,2-dichloroethylene (trans-1,2-dichloroethylene; manufactured by AXIALL CORPORATION) HFE-347pc-f; "ASAHIKLIN (registered trademark) AE-3000 )" (manufactured by Asahi Glass Co., Ltd.) HFE-569s1; "Novec (registered trademark) 7200" (manufactured by 3M Japan Co., Ltd.)

In addition, tDCE, HFE-347pc-f, HFE-467sc-f, HFE-569s1, HFE-449mec-f, HFE-449pc-f, HFE-476pcf-c, HFE-54-11mec-f, HFE-458pc -fc and HFE-55-10mec-fc were mixed at the ratio shown in Table 2 to prepare the solvent compositions of Examples 11-17.

In addition, HFE-467sc-f, HFE-449mec-f, HFE-449pc-f, HFE-476pcf-c, HFE-54-11mec-f, HFE-458pc-fc, HFE-55-10mec-fc are used respectively It is made by the method described in Japanese Patent Application Publication No. 9-263559.

(Evaluation) For the solvent composition obtained in each of the above examples, the solubility test, flammability test, and cleaning test for processing oil and asphalt were evaluated by the following methods.

<Solubility test (1)~(4)> For the solubility test (1), put 10g of the solvent composition obtained in each example into a glass spiral vial, and add the product name of the cutting oil "Daphne Magplus HT- 10" (manufactured by Idemitsu Kosan Co., Ltd.) 5g, close the lid and manually shake to mix to prepare a test solution, and then let it stand for 1 minute. In addition, the test was carried out at a temperature of 23°C. After standing still, the test solution was observed with the naked eye. As a result, the case where turbidity and separation of two layers were not observed was regarded as "A", and the case where turbidity or separation of two layers was observed was regarded as "B".

Except that the cutting oil (product name "Daphne Magplus HT-10" (manufactured by Idemitsu Kosan Co., Ltd.)) was replaced with the cutting oil shown below, the test was carried out in the same manner as the solubility test (1), and the same Benchmark to evaluate the solubility of cutting oil. Solubility test (2): Product name "Daphne Magplus AM20" (manufactured by Idemitsu Kosan Co., Ltd.) Solubility test (3): product name "Daphne Magplus HM25" (manufactured by Idemitsu Kosan Co., Ltd.) Solubility test ( 4): Product name "G-6318FK" (manufactured by Nippon Oil Corporation)

<Solubility test (5)> For the solubility test (5), a glass substrate test piece with asphalt (asphalt) attached was made from the test piece, which was sprayed with SPRAY PITCH (product name) on a 10mm×20mm×5mm glass substrate "SPRAY PITCH": Kouchong Electric Co., Ltd. product) and dry it overnight to attach asphalt (asphalt). 100 g of the solvent composition obtained in each example was put into a 100 ml glass beaker, and one test piece obtained above was immersed for 1 minute, and the degree of removal of pitch from the test piece was visually evaluated. The case where asphalt is removed from the glass substrate test piece is regarded as "A", and the case where the asphalt component remains on the glass substrate test piece is regarded as "B".

<Inflammability test> Using a Cleveland open flash point tester (manufactured by Yoshida Manufacturing Co., Ltd., model 828), it was confirmed whether 200 mL of the solvent composition obtained in each example had a flash point from 23°C to the boiling point. The results of solubility test (1)~(5) and flammability test are shown in the lower column of Table 1 and 2.

[Table 1]

[Table 2]

<Washing test; Examples 18-29> The solvent composition obtained in each of the above examples was applied to the same washing device as shown in Fig. 1 to perform a washing test. In addition, this cleaning test is an evaluation test of the above-mentioned solvent composition, and is also an example of a cleaning method using the above-mentioned solvent composition.

Prepare the solvent composition obtained in Example 1 above in the washing tank 1 (capacity: 5.2 liters), washing tank 2 (capacity: 5.0 liters), and steam generating tank 3 (capacity: 2.8 liters) of the washing device 10 . After that, the operation was continued for 8 hours without washing, so that the solvent composition of each tank in the washing device 10 was stabilized and became a stable state. In addition, for the article D to be cleaned, a small piece of SUS-304 (25mm×30mm×2mm) was immersed in the same cutting oil as that used in the solubility test (1) to prepare a test piece.

Using the cleaning device 10 in a stable state, as shown in FIG. 1, the test piece is sequentially passed through the cleaning tank 1, the rinsing tank 2, and the steam area 43 directly above the steam generating tank 3 for cleaning. At that time, the temperature of the solvent composition La in the cleaning tank 1 is set to 35°C, and the cleaning of the cleaning tank 1 is performed under an ultrasonic wave with a frequency of 40 kHz and an output of 200 W for 1 minute. Furthermore, the temperature of the solvent composition Lb in the rinsing tank 2 is set to 25°C, and the solvent composition Lc in the steam generating tank 3 is heated to keep it in a boiling state. During washing, the solvent composition Lm obtained by condensing the steam in the vapor zone 4 and removing the moisture is returned to the washing tank 2, and the overflow of the washing tank 2 flows into the washing tank 1, and then the washing tank 1 The remaining solvent composition La in the gas is sent back to the steam generating tank 3.

After the cleaning, the solvent composition La in the cleaning tank 1 and the solvent composition Lc in the vapor generation tank 3 are collected, and the composition of the collected composition is analyzed by a gas chromatograph (GC7890 manufactured by Agilent). Evaluate the flammability of each collected composition in the same way as the above flammability test.

In addition, the residual state of cutting oil on the cleaned test piece was visually observed as an evaluation of cleanability. However, the case where almost all the cutting oil is removed is regarded as "A", and the case where most of the cutting oil remains is regarded as "B".

For each solvent composition obtained in the above Examples 2-8 and 10, the cleaning test was performed in the same manner as the solvent composition of the above Example 1 to evaluate the cleaning performance and the solvent composition of each tank in a stable state. The flammability.

In addition, for each solvent composition obtained in the above Examples 11-13, a cleaning test was performed in the same manner as the solvent composition of the above Example 1 to evaluate the cleaning performance and the solvent composition of each tank in a stable state. The flammability.

Table 3 shows the example number and composition of the solvent composition prepared at the start of the operation of the cleaning device 10, and the comparison of the solvent composition La in the cleaning tank 1 and the solvent composition Lc in the steam generating tank 3 after the operation is stabilized. Evaluation results of composition, flammability and detergency. In addition, the composition [mass %] in Table 3 shows the mass% of each component in the total composition in the order of tDCE/HFE(A)/HFE(B). The composition [mass%] of the solvent composition of Example 26 is the mass% of tDCE/HFE-347pc-f.

[table 3]

As can be seen from Table 1, the solvent compositions of Examples 1 to 7 within the composition range of the solvent composition of the present invention all have excellent cutting oil solubility and no flash point. Also, as shown in Table 3, the cleaning method in which the solvent composition is accompanied by a phase change—specifically, in the cleaning method that uses the cleaning device 10 and has a solvent contact step and a vapor contact step, as the cleaning method of the present invention In Examples 18-24, the solvent compositions of Examples 1-7 that fall within the composition range of the solvent composition of the present invention are used, and the composition of the solvent composition La of the washing tank 1 is maintained at the composition of the solvent composition of the present invention It has cleaning properties within the range, and the composition of the solvent composition of each tank does not become a flammable composition, and it can operate stably.

In addition, as can be seen from Table 2, the solvent compositions of Examples 11 to 17 within the composition range of the solvent composition of the present invention all have excellent cutting oil solubility and no flash point. Also, as shown in Table 3, the cleaning method in which the solvent composition is accompanied by a phase change—specifically, in the cleaning method that uses the cleaning device 10 and has a solvent contact step and a vapor contact step, as the cleaning method of the present invention In Examples 27 to 29, the solvent composition of Examples 11 to 13 within the composition range of the solvent composition of the present invention is used, and the composition of the solvent composition La of the washing tank 1 is maintained at the composition of the solvent composition of the present invention It has cleaning properties within the range, and the composition of the solvent composition of each tank does not become a flammable composition, and it can operate stably.

Examples 8 and 9 outside the composition range of the solvent composition of the present invention either have good solubility but have a flash point, or they do not have a flash point but have insufficient solubility (Table 1). As can be seen from Table 3, Examples 25 and 26, which are not within the scope of the cleaning method of the present invention, use the solvent compositions of Examples 8 and 10 that are outside the composition range of the solvent composition of the present invention. The solvent composition is accompanied by a phase change. Some of the cleaning methods do not satisfy any of the cleaning properties and the flammability. The cleaning method of Example 26 (using the solvent composition of Example 10) has cleaning properties and is not a flammable composition at the time of preparation. However, during the operation of the cleaning device 10, a flammable composition is formed in the steam generating tank 3 The result of the solvent composition Lc. Therefore, the solvent composition of Example 10 is difficult to use in this cleaning method accompanied by phase change.

[Examples 30 to 36: Composition for coating film formation] The solvent composition obtained in Example 2 and the product name of the fluorine-based lubricant "Krytox (registered trademark) GPL102" (manufactured by DuPont Co., Ltd., fluorine-based oil) were mixed, A lubricant solution with a lubricant content of 0.5% by mass based on the total lubricant solution was prepared. Also, "Shin-Etsu Silicone KF-96" (manufactured by Shin-Etsu Chemical Co., Ltd., silicone oil) of silicone-based lubricants can be used instead of fluorine-based lubricants, and then the lubricant solution can be prepared in the same manner as above. .

Except that the solvent composition of Example 2 was replaced with the solvent composition of Example 5, in the same manner as described above, each solvent composition was prepared to contain fluorine-based lubrication in the ratio shown in Table 4 to the total amount of the lubricant solution. Two kinds of lubricant solutions of lubricants and silicone-based lubricants. In the solvent composition of Example 11, a lubricant solution containing only a fluorine-based lubricant was prepared in the same manner as described above. For the solvent compositions of Examples 14 and 16, only the lubricant solution of the silicone lubricant was prepared in the same manner as described above.

(Evaluation) The solubility of the lubricant solution obtained in each of the above examples, the drying property at the time of coating film formation, and the uniformity of the obtained coating film were evaluated. <Solubility> The lubricant solution of each example obtained above was visually observed and the dissolution state of the lubricant was evaluated. The evaluation of solubility is carried out at a temperature of 23°C. The case where turbidity and two-layer separation are not observed in the lubricant solution is regarded as "A", and the case where turbidity or two-layer separation is observed is regarded as "B".

<Drying property, uniformity of coating> The surface of an aluminum vapor-deposited sheet with aluminum vapor-deposited on an iron sheet is coated with the lubricant solution obtained in each of the above examples with a thickness of 0.4mm, and dried at 19-21°C. A lubricant coating film is formed on the surface of the aluminum vapor-deposited plate. The state of the lubricant coating film obtained is observed with the naked eye. If there is no unevenness or defect and a uniform coating film is formed, it is regarded as "A", and if there is unevenness or defect, it is regarded as "B". In addition, the dryness of the lubricant solution when the lubricant coating film is formed is observed with the naked eye. The case where the solvent dries quickly is regarded as "A", and the case where the solvent is not dried is regarded as "B". The evaluation results are shown in Table 4 together with the lubricant solution composition.

[Table 4]

As can be seen from Table 4, the examples of the coating film forming compositions of Examples 30 to 36 are the solvent compositions of Examples 2, 5, 11, 14, and 16 within the composition range of the solvent composition of the present invention. All of them are excellent The solubility of lubricating oil, and the formation of a uniform coating film, has good drying properties.

1‧‧‧Washing tank 2‧‧‧Running tank 3‧‧‧Steam generating tank 4, 43‧‧‧Vapor zone 5‧‧‧Water separation tank 6,7‧‧‧Heater 8‧‧‧Ultrasonic wave Vibrator 9‧‧‧Cooling pipe 10‧‧‧Cleaning device 11,12,14‧‧‧Piping 13‧‧‧Arrow D‧‧‧Items to be washed La, Lb, Lc, Lm‧‧‧Solvent composition

Fig. 1 is a diagram schematically showing an example of a cleaning device for performing the cleaning method of the present invention.

1‧‧‧Washing tank

2‧‧‧Washing tank

3‧‧‧Steam generating tank

4. 43‧‧‧Vapor zone

5‧‧‧Water separation tank

6, 7‧‧‧ heater

8‧‧‧Ultrasonic Vibrator

9‧‧‧Cooling pipe

10‧‧‧Cleaning device

11, 12, 14‧‧‧Piping

13‧‧‧Arrow

D‧‧‧Items to be washed

La, Lb, Lc, Lm‧‧‧solvent composition

Claims (10)

A solvent composition containing: trans-1,2-dichloroethylene, a first hydrofluoroether with a boiling point of 40-65°C, and a second hydrofluoroether with a boiling point of 70-120°C; the aforementioned first hydrofluoroether The ether contains selected from 1,1-difluoroethyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl At least one of the group consisting of ether and 1,1-difluoroethyl-2,2,3,3,3-pentafluoropropyl ether; and, relative to trans-1,2-dichloroethylene , The total amount of the aforementioned first hydrofluoroether and the aforementioned second hydrofluoroether, the ratio of trans-1,2-dichloroethylene is 65~80% by mass, and the ratio of the aforementioned first hydrofluoroether is 5-25% by mass , The ratio of the aforementioned second hydrofluoroether is 5-25% by mass. The solvent composition of claim 1, wherein the aforementioned second hydrofluoroether contains at least one selected from the group consisting of: ethoxynonafluorobutane, 1,1,2,3,3, 3-hexafluoropropyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3,3-pentafluoropropyl ether, 1, 1-Difluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl-2,2,3,3,3-pentafluoro Propyl ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl-2, 2,3,3-Tetrafluoropropyl ether and 3-methoxy-4-trifluoromethyl-1,1,1,2,2,3,4,5,5,5-decafluoropentane. The solvent composition of claim 1 or 2, wherein the aforementioned first hydrofluoroether is 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, and the aforementioned second hydrofluoroether It is ethoxy nonafluorobutane, and is relative to trans-1,2-dichloroethylene, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether and ethoxy Nonafluorobutane The total amount of alkanes, the ratio of trans-1,2-dichloroethylene is 65~80% by mass, the ratio of 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether It is 5-25% by mass, and the ratio of ethoxynonafluorobutane is 5-25% by mass. Such as the solvent composition of claim 1 or 2, wherein the ratio of the total amount of trans-1,2-dichloroethylene, the first hydrofluoroether and the second hydrofluoroether relative to the total amount of the aforementioned solvent composition is 90-100% by mass. For example, the solvent composition of claim 1 or 2, which is used to clean the dirt of the cleaned item. A washing method, characterized in that the solvent composition of claim 5 is brought into contact with the article to be washed. A composition for forming a coating film, which contains the solvent composition according to any one of claims 1 to 4 and a non-volatile organic compound. The composition for forming a coating film according to claim 7, wherein the aforementioned non-volatile organic compound is a lubricant. The composition for forming a coating film according to claim 8, wherein the lubricant is at least one selected from the group consisting of silicone lubricants and fluorine lubricants. A method for forming a coating film, characterized in that: after coating the composition for forming a coating film according to any one of claims 7 to 9 on an object to be coated, the solvent composition is evaporated to form the non-volatile Coating film composed of organic compounds.

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